EP0714654B1 - Composition and process for permanent waving of hair - Google Patents

Description

The present invention relates to diquaternary Polysiloxanes containing Permanent shaping agent and a method for permanent hair deformation using this Medium.

Hair is in its morphological structure of Hairline different from hair tips. This is based inter alia on environmental influences (for example the sun or other weather conditions) as well as chemical, mechanical treatments (For example, combing or blow drying, permanent wave or Dyeing treatments, shampooing) that the hair in the course of is subject to his lifetime. These outer ones Actions as well as age-related morphological Changes in the hair cause an increased static Charging the hair, a deteriorated combability, a rough and unpleasant grip, a diminished one Gloss as well as increasing brittleness of the hair and can in extreme cases cause a rupture of the hair while or after a permanent deformation treatment.

Several attempts have already been made To solve problems. So for example the use became from usable in the acidic to neutral pH range Thioglycolic acid ester based permanent shaping agents recommended. Through the use of permanent shaping agents On thioglycol ester basis is indeed a relatively even and gentle deformation of the hair scored from the hairline to the hair tips, however are the physiological and especially sensitizing Properties of thioglycolic acid ester not satisfactory, so that the use of other physiological better tolerated reducing agents instead Thioglykolsäureester is desirable. Likewise is recommended in the literature, permanent shaping agents cationic polymers and / or cationic surfactants to add, whereby a good combability of the hair and a pleasant grip of the hair should be achieved. It However, it has been found that when using this Means an uneven deformation of the hair (strong Deformation in the area of the hair tips / weak deformation in the area of the hairline).

So z. For example, GB-A 2 197 352 discloses a permanent waving agent which comprises (A) an amino acid and (B) a water-soluble or emulsifiable silicone compound in an amount which is sufficient to provide improved wave stability. One under the Trade name ABIL®B 9905 sold by the manufacturer Th. Goldschmidt AG suitable monoquaternary silicone compound is on page 4 lines 37 to 55 as Structural formula listed. For the task, to improve the well stability, it is preferred to use nonionic and water-soluble dimethicone copolyols (see S.3 Z.32 to S.4 Z.35).

Furthermore, in WO-A 94/21224 the use of non-volatile Organopolysiloxanes in combination with trimethylammonium methacrylate homopolymer or its copolymer with acrylamide in cosmetic products for the skin and Hair treatment recommended (claim 1). The hair treatment products can be used as Shampoos or rinses u. a. applied before, after or between a perm (see p.7, pages 26-33). As a suitable nonvolatile organopolysiloxanes is a large number of very different nonionic and cationic compounds (see p.2 Z.33 to p.6 Z.12). As examples of organopolysiloxanes with quaternary groups become u. a. on page 6 in paragraph 3 under h) the Tradenames X28108, X28109 and ABIL K 3270 are cited.

DE-C 37 19 086 relates to the quaternary organopolysiloxanes having two terminal Ammonium groups of the formula (I) of the present application, their preparation and their use in cosmetic preparations for hair care (cf. Claims 1 to 3). The task is to find connections with improved use properties, which in particular the care of the hair improve (see p.5 Z.22-23). Another advantage can be found on page 12 in Line 24, the improved wet and dry combability and improved gloss of the Hair. The use of the perm is not mentioned; accordingly also the problem of uneven permanent deformation from the hairline to the Hair tips not discussed.

It was therefore the task of a Dauerverformungsverfahren and suitable means for carrying out this To provide a method by which a gentle and even permanent deformation of the hair from the hairline to the hair ends at the same time good physiological compatibility (especially with regard to sensitization risk).

Surprisingly, it has now been found that the The task described above in an excellent way by the use of diquaternary polysiloxanes Permanent shaping agents is solved.

wobei
Z der Rest

ist,

R¹, R², R³ = Alkylreste mit 1 bis 22 Kohlenstoffatomen oder Alkenylreste mit 2 bis 22 Kohlenstoffatomen, wobei die Alkyl- oder Alkenylreste Hydroxylgruppen aufweisen können und mindestens einer der Reste R¹, R², R³ mindestens 10 Kohlenstoffatome aufweist,

R⁴, R⁵, R⁷, R⁹, R¹⁰ = Alkylreste mit 1 bis 22 Kohlenstoffatomen oder Alkenylreste mit 2 bis 22 Kohlenstoffatomen, wobei die Alkyl- oder Alkenylreste Hydroxylgruppen aufweisen können,

R⁶ = -O- oder NR⁸-Rest, R⁸ = Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen oder Wasserstoffrest,

x = 2 bis 4,

M = ein zweiwertiger Rest, ausgewählt aus der Gruppe

wobei das N-Atom des Restes Z mit dem Rest M über das zur C-OH-Gruppe im Rest M benachbarte Kohlenstoffatom verbunden ist,

n = eine Zahl von 0 bis 200,

X^- = anorganisches oder organisches Anion, das von einer üblichen physiologisch verträglichen Säure HX herrührt,

enthält.The present invention therefore provides a means for permanent deformation of hair on the basis of a keratin-reducing compound, which
characterized in that it comprises a diquaternary polysiloxane of the general formula (I)

in which
Z the rest

is

R ¹ , R ² , R ³ = alkyl radicals having 1 to 22 carbon atoms or alkenyl radicals having 2 to 22 carbon atoms, where the alkyl or alkenyl radicals may have hydroxyl groups and at least one of the radicals R ¹ , R ² , R ^{3 has} at least 10 carbon atoms,

R ⁴ , R ⁵ , R ⁷ , R ⁹ , R ¹⁰ = alkyl radicals having 1 to 22 carbon atoms or alkenyl radicals having 2 to 22 carbon atoms, where the alkyl or alkenyl radicals may have hydroxyl groups,

R ⁶ = -O- or NR ⁸ radical, R ⁸ = alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms or hydrogen radical,

x = 2 to 4,

M = a bivalent radical selected from the group

wherein the N atom of the radical Z is connected to the radical M via the carbon atom adjacent to the C-OH group in the radical M,

n = a number from 0 to 200,

X ^- = inorganic or organic anion which results from a customary physiologically acceptable acid HX,

contains.

M = -(CH₂)₃-O-CH₂-CH(OH)-CH₂-;

R⁴, R⁵ = CH₃;

R⁶ = NH-Rest; R⁷ = Kokosfettsäurerest; x = 3; n = 10 oder 30 und X^- = Acetatanion.

Among the diquaternary polysiloxanes of the formula (I), the compounds in which

M = - (CH ₂ ) ₃ -O-CH ₂ -CH (OH) -CH ₂ -;

R ⁴ , R ⁵ = CH ₃ ;

R ⁶ = NH radical; R ⁷ = coconut fatty acid residue; x = 3; n = 10 or 30 and X ^- = acetate anion.

The composition of the permanent shaping agent according to the invention corresponds to those for such funds each known preparation methods based on keratin-reducing Links.

The diquaternary polysiloxane of formula (I) is in this Permanent shaping agent preferably in an amount of 0.02 to 5 percent by weight (based on the total amount the ready-to-use preparation), with a Amount of 0.05 to 5 weight percent is particularly preferred is.

The permanent shaping agent according to the invention can in a Variety of preparation methods are used by hereinafter some preferred modes of preparation be explained in more detail.

In the means for permanent deformation of hair in particular, it is aqueous, slightly acidic Alkaline (pH = 6 to 10) set preparations, which is a keratin-reducing compound, for example Mercaptocarboxylic acids such as thioglycolic acid and Thiolactic acid or its salts and 2-hydroxy-3-mercaptopropionic acid, Cysteine or its salts and derivatives; Cysteamine or its salts and derivatives and sulfurous Acid or its salts, alone or in combination with each other, included. The use concentration of keratin-reducing compound is about 2 to 25% by weight, preferably 5 to 18% by weight. The required pH is predominantly through the addition of ammonia and organic amines as well Ammonium and alkali carbonate or bicarbonate set.

The means for permanent deformation of hair can both in the form of an aqueous solution or emulsion as also in thickened form on an aqueous basis, in particular as a gel, cream or paste.

Of course, the deformation means all for such agents conventional and known additives, for Example, thickener, such as kaolin, Bentonite, fatty acids, higher fatty alcohols, starch, Polyacrylic acid and its derivatives, cellulose derivatives, Alginates, vaseline or paraffin oil; Wetting agent or Emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surfactant Substances, for example fatty alcohol sulphates, Fatty alcohol ether sulfates, alkyl sulfonates, alkyl benzene sulfates, quaternary ammonium salts, alkyl betaines, ethoxylated Fettsäurester; further opacifiers, such as Polyethylenglykolester; or alcohols, such as Ethanol, propanol, isopropanol or glycerol, Solubilizing agents; stabilizers; Buffer substances; Perfume oils, Dyes and hair conditioning and hair care Ingredients, such as lanolin derivatives, Cholesterol, pantothenic acid or betaine. The The ingredients mentioned are used for such purposes usual amounts used, for example, the wetting agents and emulsifiers in concentrations of 0.2 to 30 weight percent, while the thickener in in an amount of 0.5 to 20% by weight in this Means may be included.

Furthermore, this means of increasing the so-called Swelling and penetration substances, such as Dipropylene glycol monomethyl ether, 2-pyrrolidone or imidazolidin-2-one, in an amount of 0.5 to 20% by weight as well as to avoid overfilling the hair Dithio compounds, for example dithiodiglycolic acid, Dithiodimilchsäure or their salts can be added.

By varying the pH can be a means available which is universal for every hair structure, optionally with additional heat, suitable is. The agent causes a elastic, permanent and uniform deformation of the Hair from the hairline to the hair tip without allergic or cause sensitizing reactions. In particular The deformation is in the area of the hairline improved and a Überkrausung the hair tips in the Comparison to the hairline avoided as well as the shine and improved the combability of the hair.

The present invention further relates to a method for permanent deformation of hair, in which one the hair before and / or after you have it in the desired Form brings, treated with a deformation agent, with Water rinses, then treated by oxidation, with water flushes, if necessary, to the water wave lays and then dries, which is characterized in that as Deformation means the invention described above Medium is used.

According to the method of the invention, the hair can first washed with a shampoo and then with water be rinsed. Subsequently, the towel-dried Split hair into single strand and use on winder a diameter of 5 to 30 millimeters, preferably 5 up to 15 millimeters, wound. Then the hair is with a sufficient amount for the hair deformation, preferably 60 to 120 grams, of the invention described Treated deforming agent.

After one for the permanent deformation of the hair sufficient exposure time, which depends on the condition of the hair, the pH and the deformation efficiency the deforming agent and depending on the application temperature 5 to 30 minutes (10 to 30 minutes without heat; 5 to 20 minutes with heat) is, the hair is rinsed with water and then oxidatively aftertreated ("fixed"). The aftertreatment agent is, depending on hair, preferably in a quantity of 80 to 100 grams, used.

For oxidative aftertreatment, any, previously used for such treatment, aftertreatment agent be used. Examples of in such aftertreatment agents usable oxidizing agents are potassium and sodium bromate, sodium perborate, Urea peroxide and hydrogen peroxide. The concentration of the oxidizing agent is dependent on the Application time (usually about 5 to 15 minutes) and the application temperature varies. Usually the oxidizing agent is in the ready to use aqueous aftertreatment agent in a concentration of 0.5 to 10 weight percent before. The means for the Of course, further oxidative treatment can be added Substances, such as wetting agents, care substances such as cationic polymers, weak acids, buffer substances or peroxide stabilizers, and in the form of a aqueous solution, an emulsion and in thickened form on an aqueous basis, especially as a cream, gel or Paste, present.

Then the winder is removed. If necessary, The unwound hair can be oxidative again be treated. Then the hair is rinsed with water, optionally placed to the water wave and finally dried.

The following examples are intended to explain the invention in more detail, without wishing to limit these to the examples. Example 1: permanent shaping agent for normal hair 11.9 g ammonium thioglycolate 5.0 g ammonium 1.0 g with 4 moles of ethylene oxide ethoxylated lauryl alcohol 0.5 g Ammonia (25% aqueous solution) 0.5 g cocoamidopropyl 0.5 g perfume oil 2.0 g Diquaternary polysiloxane according to formula (I) (trade name :: ABIL® -QUAT 3270 from Th. Goldschmidt AG, Essen / FRG) 0.1 g Vinylpyrrolidone / styrene copolymer (trade name :: ANTARA® 430 from GAF Corp., New York / USA) 78.5 g water 100.0 g

The pH of this permanent shaping agent is 8.3. Normal, undamaged hair is washed, toweled with a towel, and then wound on 6-millimeter winder. The hair is then moistened uniformly with the permanent shaping agent described above and rinsed thoroughly with water after an exposure time of 18 minutes at room temperature. The hair is then oxidatively treated with 80 grams of a 3 percent aqueous hydrogen peroxide solution, rinsed again with water, placed in a water wave and dried. The hair treated in this way has a very even and lively frill. Example 2: Permanent shaping agent for normal and difficultly deformable hair 14.2 g ammonium thioglycolate 5.5 g ammonium 3.0 g 1,2-propanediol 1.2 g castor oil ethoxylated with 40 moles of ethylene oxide 1.0 g Ammonia (25% aqueous solution) 0.8 g perfume oil 0.5 g Poly (dimethyldiallylammonium chloride) 0.3 g Vinylpyrrolidone / styrene copolymer (trade name: ANTARA® 430 from GAF Corp., New York / USA) 1.0 g Diquaternary polysiloxane of the formula (I) (trade name: ABIL®-QUAT 3270 from Th. Goldschmidt AG, Essen / FRG) 72.5 g water 100.0 g

The pH of this agent is 8.5.

The application of the permanent shaping agent takes place in the manner described in Example 2, but the exposure time of the permanent shaping agent is 20 minutes. It will receive a natural-looking, uniform deformation of the hair from the hairline to the hair tips. Example 3: Permanent shaping agent for dyed hair 9.1 g ammonium thioglycolate 2.5 g ammonium 1.0 g castor oil ethoxylated with 40 moles of ethylene oxide 1.0 g Poly (dimethyldiallylammonium chloride) 1.0 g cocobetaines 0.6 g perfume oil 0.4 g Ammonia (25% aqueous solution) 3.0 g diquaternary polysiloxane of the formula (I) (trade name :: ABIL® -QUAT 3270 from Th. Goldschmidt AG, Essen / FRG) 81.4 g water 100.0 g

The pH of this agent is 8.0.

Hair which has been damaged by dyeing treatments is washed with a mild shampoo, dried with a towel and wound on winder with a diameter of 8 millimeters. Subsequently, the permanent shaping agent described above is uniformly distributed on the wound hair. After a reaction time of 15 minutes at room temperature, the wrapped hair is rinsed with water and slightly dried with a towel. Then the wound hair is treated oxidatively with a 2.5 percent aqueous hydrogen peroxide solution. After a contact time of 5 minutes, the winder are removed, the hair rinsed with water, then toweled with a towel, put on a hairstyle and dried.
As a result, a uniform, elastic and permanent deformation of the hair is obtained. Example 4: Permanent shaping agent for dyed hair 12.0 g cysteine hydrochloride 4.2 g ammonium thioglycolate 6.0 g Ammonia (25% aqueous solution) 3.0 g 1,2-propanediol 3.0 g 1,2-butanediol 3.0 g Copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate quaternized with diethyl sulfate (20% aqueous solution, trade name: GAFQUAT® 755 from GAF Corp., New York / USA) 2.0 g ammonium 0.8 g cocoamidopropyl 2.0 g diquaternary polysiloxane of the formula (I) (trade name :: ABIL®QUAT 3270 from Th. Goldschmidt AG, Essen / FRG) 0.1 g Vinylpyrrolidone / styrene copolymer (trade name :: ANTARA® 430 from GAF Corp., New York / USA) 63.9 g water 100.0 g

The pH of this permanent shaping agent is 8.2. The hair is in the manner described in Example 4 treated, wherein the exposure time of the permanent shaping agent 15 minutes.

The hair treated in this way has a uniform Krause, whose curls have a good elasticity and bounce respectively.

R4, R5

= CH₃

x

= 3

R6

= NH-Rest

R7

= Kokosfettsäurerest

n

= 10

X^-

= Acetatanion

As diquaternary polysiloxane (trade name: ABIL® -QUAT 3270), Examples 1 to 5 used a compound of the formula (I) in which

R4, R5

= CH ₃

x

= 3

R6

= NH radical

R7

= Coconut fatty acid residue

n

= 10

X ^-

= Acetate anion

Example 5: Comparative Experiments

For the comparative experiments count hair strands, consisting of 100 hairs of the same quality, on wound spiral winder and with the inventive Means treated in the usual way. To an exposure time of the permanent deformation of 10 minutes at 45 degrees Celsius, the hair with Rinsed water and then treated by oxidation. To The strands of hair were removed from the winders during drying and in a 40 degrees Celsius warm water bath hanged.

l_o =

Länge der gestreckten Haarsträhne

l_t =

Länge der ausgehängten Haarsträhne nach t = 0, 10, 60, 120, 240 oder 360 Minuten

l₁ =

Länge der verformten, aufgewickelten Haar strähne

Subsequently, the total length of the hair strand as well as the length of the individual curls was measured at certain intervals (after 0, 10, 60, 120, 240, 360 minutes). From the total length of the hair strand, the wave stability ("Curl retention") was calculated according to the following formula: Well stability [%] = (Lo-l t ) • 100 (Lo-l 1 ) With

l _o =

Length of the stretched strand of hair

l _t =

Length of the detached strand of hair after t = 0, 10, 60, 120, 240 or 360 minutes

l ₁ =

Length of the deformed, wound hair strand

Well stability is a measure of the effectiveness of a Permanent shaping device and the durability of a perm. The length of a curl turn is the following called Krausenstärke [mm / Locke]. She stops good measure for the characterization of the curl image, because they are the visual impression of a curl image very well reproduces. A small value for Krausenstärke means Here is a small-scaled Wellbild.

The corrugating stability and Krausenstärke with a mild alkaline permanent shaping agent of the following composition 11.9 g ammonium thioglycolate 5.0 g ammonium 5.0 g Polymer (a) to (g) 1.0 g with 4 moles of ethylene oxide ethoxylated lauryl alcohol 0.5 g Ammonia (25% aqueous solution) 0.5 g cocoamidopropyl 0.5 g perfume oil 75.6 g water 100.0 g treated hair was measured for the hairline and hair tips respectively.

The pH of the permanent shaping agent used is 8.3.

(a) Polyquaternium-6 (Poly(diallyldimethylammoniumchlorid)

(b) Polyquaternium-16 (Copolymer aus Vinylimidazoliummethochlorid und Vinylpyrrolidon)

(c) CROQUAT® WKP der Firma Croda/BRD (quaternisiertes Eiweißhydrolysat)

(d) Dow Corning® 929-Cationic Emulsion der Dow Corning Europe/Belgien (kationische Emulsion aus Amodimethicone, Tallowtrimonium Chloride und Nonoxynol-10)

(e) Pecosil SMQ-40 der Phoenix Chemical Inc./USA (Dimethicone Copolyol Phospho Myristyl Ammonium Chloride)

(f) Pecosil SWP Q 40 der Phoenix Chemical Inc. USA (quaternäres Eiweißhydrolysat/Dimethicone Copolyol Phosphat)

(g) Abil® -Quat 3270 (diquaternäres Polysiloxan gemäß Formel (I)).

The following compounds were used as polymers:

(a) Polyquaternium-6 (poly (diallyldimethylammonium chloride)

(b) Polyquaternium-16 (copolymer of vinylimidazolium methochloride and vinylpyrrolidone)

(c) CROQUAT® WKP from Croda / Germany (quaternized protein hydrolyzate)

(d) Dow Corning® 929 Cationic Emulsion from Dow Corning Europe / Belgium (cationic emulsion of amodimethicone, tallowtrimonium chlorides and nonoxynol-10)

(e) Pecosil SMQ-40 of Phoenix Chemical Inc./USA (Dimethicone Copolyol Phospho myristyl Ammonium Chloride)

(f) Pecosil SWP Q 40 from Phoenix Chemical Inc. USA (Quaternary Protein Hydrolyzate / Dimethicone Copolyol Phosphate)

(g) Abil® Quat 3270 (diquaternary polysiloxane according to formula (I)).

The following table summarizes the results of the measurement of the corrugation stabilities after a hang-up time of t = 360 minutes for the hair strands treated with the permanent shaping agent described above. Wellstabilitäten depending on the polymer used polymer Well stability in the area of the hairline [%] Well stability in the area of the hair tips [%] Difference of the corrugated stability in the area of the hair tips and the hairline [%] without polymer additive 39.8 43.4 3.6 (A) 36.9 51.8 14.9 (B) 38.1 49.2 11.1 (C) 41.1 46.9 5.8 (D) 37.2 46.9 9.7 (E) 38.7 43.8 5.1 (F) 44.1 47.1 3.0 (G) 47.0 45.0 -2.0

From Table 1 it is clear that when used of the permanent shaping agent (g) according to the invention Difference between the well stabilities in the range of Hairline and hair tips are the least and no "Überkrausung" of the hair tips takes place, but the deformation of the hair in the area of the hairline even slightly stronger than in the area of Hair tips.

This result is further clarified by the following Figure 1.

In contrast to the agent according to the invention (g) show the remaining permanent deformation means depending on the used Polymer a greater and lesser difference in the Wellstabilitäten in the area of the hair tips and the hairline, this problem especially when using of Polyquaternium-6 (a). As a result of these differences in the well stabilities in the The area of the hair tips and the hairline is at the non-inventive means a restless and uneven Obtained deformation result, which sometimes even worse than when using a polymer-free permanent shaping agent.

Another exact way of assessing the deformation result in the area of the hairline and the hair tips is next to the corrugated stability the Krausenstärke. The following Table 2 gives an overview of the differences determined with respect to the Krausenstärke for the hairline and for the hair tips. Difference in Krausenstärken in the area of the hairline and hair tips polymer Difference in Krausenstärke [mm] without polymer additive 3.58 (A) 8.83 (B) 5.95 (C) 4.69 (D) 5.40 (E) 6.43 (F) 4.12 (G) 1.60

The facts should be clarified by the following Figure 2.

It is clear from Table 2 and Figure 2 that in the non-inventive deformation means the Krausenstärke in the hair tips significantly smaller is as in the area of the hairline. This means that the curl image from the hairline to the hair tips always kleinlockiger becomes. Such curls work very much restless and generated in particular by the small curls the hair tips the impression of a Überkrausung the Hair.

In contrast, the Krausenstärke in use of the deforming agent (g) according to the invention in the range the hairline and hair tips are almost identical, whereby a uniform curl image is obtained, the also a good wave result in the area of the hairline having.

All percentages given in the present application Unless otherwise specified, weight percent represents.

Claims (5)

1. Agent for the permanent shaping of hair based on a keratin-reducing compound, characterised in that it contains a diquaternary polysiloxane of the general formula (I)

   

   wherein
   Z is the residue

   

   R¹, R², R³ = alkyl residues having from 1 to 22 carbon atoms or alkenyl residues having from 2 to 22 carbon atoms, wherein the alkyl or alkenyl residues may contain hydroxy groups and at least one of the residues R¹, R², R³ contains at least 10 carbon atoms,

   R⁴, R⁵, R⁷, R⁹, R¹⁰ = alkyl residues having from 1 to 22 carbon atoms or alkenyl residues having from 2 to 22 carbon atoms, wherein the alkyl or alkenyl residues may contain hydroxy groups,

   R⁶ = an -O- or NR⁸ residue, R⁸ = an alkyl or hydroxyalkyl residue having from 1 to 4 carbon atoms or a hydrogen residue,

   x = 2 to 4,

   M = a divalent residue selected from the group

   

   

   

   

   

   

   wherein the nitrogen atom of the resudue Z is bonded to the residue M by way of the carbon atom adjacent to the C-OH group in the residue M,

   n = an integer from 0 to 200,

   X^- = an inorganic or organic anion which originates from a customary physiologically compatible acid HX.
2. Agent according to Claim 1, characterised in that the keratin-reducing compound is selected from thioglycolic acid or its salts, thiolactic acid or its salts, 2-hydroxy-3-mercaptopropionic acid or its salts, cysteine or its salts and derivatives, cysteamine or its salts and derivatives, and sulphurous acid or its salts.
3. Agent according to any one of Claims 1 or 2, characterised in that the diquaternary polysiloxane is selected from compounds of formula (I) wherein
   M =-(CH₂)₃-O-CH₂-CH(OH)-CH₂-;

   

   R⁴, R⁵ = CH₃;

   R⁶ = a -NH residue; R⁷ = a coconut fatty acid residue; x = 3;

   n = 10 or 30 and X^- = an acetate anion.
4. Agent according to any one of Claims 1 to 3, characterised in that the diquaternary polysiloxane of the formula (I) is present in an amount of from 0.02 to 5% by weight.
5. Process for the permanent shaping of hair, in which the hair, before and/or after it has been brought into the desired shape, is treated with a shaping agent, rinsed with water, optionally arranged in a water wave and then dried, characterised in that an agent according to Claim 1 or 2 is used as the shaping agent.